Synthesis of crystalline ZSM-35

ABSTRACT

This invention relates to a new form of crystalline material identified as having the structure of ZSM-35, to a new and useful method for synthesizing said crystalline material and to use of said crystalline material prepared in accordance herewith as a catalyst for organic compound, e.g. hydrocarbon compound, conversion.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a new and useful method for synthesizing ahighly siliceous form of crystalline ferrierite-type material identifiedas having a ZSM-35 structure, the new ZSM-35 synthesized, and use of thecrystalline material synthesized in accordance herewith as a catalystcomponent for organic compound, e.g. hydrocarbon compound, conversion.

More particularly, this invention relates to a method for preparing thecrystalline ZSM-35 structure whereby synthesis is facilitated andreproducible and the product exhibits high purity and catalytic utility.

2. Discussion of the Prior Art

Ferrierite is a naturally occurring zeolite with an intersecting 10-ringby 8-ring structure. ZSM-35 is shown to be synthesized from reactionmixtures containing ethylene diamine or pyrrolidine directing agent inU.S. Pat. Nos. 4,016,245 and 4,107,195. Synthetic ferrierite is directedfrom a certain reaction mixture in U.S. Pat. No. 4,000,248 containingN-methylpyridinium; and another reaction mixture containing choline inU.S. Pat. No. 4,046,859. Piperidine is the directing agent in U.S. Pat.No. 4,251,499 for synthetic ferrierite. U.S. Pat. Nos. 4,323,481 and4,390,457 teach synthesis of ferrierite from reaction mixturescomprising directing agents of 2,4-pentanedione and 2-aminopyridine,respectively. U.S. Pat. No. 4,377,502 shows morpholine or dioxane usedas directing agent for ferrierite synthesis. U.S. Pat. No. 4,584,286teaches a method for synthesis of ZSM-35 from a reaction mixturecomprising bis(N-methylpyridyl) ethylinium as directing agent. Both U.S.Pat. Nos. 4,578,259 and 4,695,440 show use of pyridine plus ethyleneglycol as directing agent for synthetic ferrierite; and both U.S. Pat.Nos. 4,721,607 and 4,855,270 show use of pyridine plus ethylene diamineand ethanol as directing agent for synthetic ferrierite. U.S. Pat. No.4,925,548 teaches synthesis of ZSM-35 with hexamethyleneimine directingagent.

The above disclosures are incorporated herein by reference as to ZSM-35,synthetic ferrierite and their synthesis.

Various organic directing agents are taught for synthesis of variouscrystalline materials. For example, U.S. Pat. No. 4,139,600 teaches amethod for synthesis of zeolite ZSM-5 from a reaction mixturecomprising, as a directing agent, an alkyldiamine. U.S. Pat. No.4,296,083 claims synthesizing zeolites characterized by a ConstraintIndex of 1 to 12 and an alumina/silica mole ratio of not greater than0.083 from a specified reaction mixture containing an organicnitrogen-containing cation provided by an amine identified as beingselected from the group consisting of triethylamine, trimethylamine,tripropylamine, ethylenediamine, propanediamine, butanediamine,pentanediamine, hexanediamine, methylamine, ethylamine, propylamine,butylamine, dimethylamine, diethylamine, dipropylamine, benzylamine,aniline, pyridine, piperidine and pyrrolidine.

Piperidine is disclosed as an organic directing agent for mordenitesynthesis by P. A. Jacobs and J. A. Martens, Studies of Surface Scienceand Catalysis, 33, 12 (1987); and 2-amino-pyridine is taught for thispurpose in U.S. Pat. No. 4,390,457. Tetra-n-propylammonium salts aretaught to be mordenite directing agents in U.S. Pat. Nos. 4,707,345 and4,788,380.

U.S. Pat. No. 4,151,189 claims a method for synthesizing zeolites ZSM-5,ZSM-12, ZSM-35 and ZSM-38 containing an organic nitrogen cation from aspecified reaction mixture containing a primary amine having 2 to 9carbon atoms as a directing agent. U.S. Pat. No. 4,341,748 showssynthesis of ZSM-5 structure from reaction mixtures comprising ethanol,ZSM-5 seeds, ethanol and seeds, ethanol and ammonium hydroxide, andethanol, ammonium hydroxide and ZSM-5 seeds. U.S. Pat. No. 4,100,262teaches synthesis of ZSM-5 from a reaction mixture comprising atetraalkylammonium source and a tetraureacobalt (II) complex.

Lok et al. (3 Zeolites, 282-291 (1983)) teach numerous organic compoundswhich act as directing agents for synthesis of various crystallinematerials, such as, for example, ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-35,ZSM-48, AlPO₄ -5, AlPO₄ -8, AlPO₄ -20 and others. The article does notshow the presently required organic for synthesis of ZSM-35. The articledoes show that cyclohexylamine, N-methylcyclohexylamine,dicyclohexylamine and ethyl-n-butylamine may direct synthesis of AlPO₄-5 (U.S. Pat. No. 4,310,440).

The zeolitic compositions labeled PSH-3 in U.S. Pat. No. 4,439,409 aresynthesized from reaction mixtures containing hexamethyleneimine asdirecting agent. U.S. Pat. No. 4,954,325 utilizes hexamethyleneimine inanother reaction mixture to direct synthesis of MCM-22. That organic isused in U.S. Pat. No. 4,981,663 for synthesis of yet another crystallinestructure labelled MCM-35. As mentioned above, ZSM-35 is directed bythis same compound in U.S. Pat. No. 4,925,548.

Other publications teaching various organic directing agents forsynthesis of various crystalline materials include, for example, U.S.Pat. No. 4,592,902, teaching use of an alkyltropinium directing agent,alkyl being of 2 to 5 carbon atoms, for synthesis of ZSM-5; U.S. Pat.No. 4,640,829, teaching use of dibenzyldimethylammonium directing agentfor synthesis of ZSM-50; U.S. Pat. No. 4,637,923, teaching use of (CH₃)₂(C₂ H₅)N⁺ (CH₂)₄ N⁺ (C₂ H₅)(CH₃)₂ directing agent for synthesis ofanother novel zeolite; U.S. Pat. No. 4,585,747, teaching use of bis(N-methylpyridyl) ethylinium directing agent for synthesis of ZSM-48;U.S. Pat. No. 4,585,746, teaching use of bis (N-methylpyridyl)ethylinium directing agent for synthesis of ZSM-12; U.S. Pat. No.4,584,286, mentioned above, teaching use of bis (N-methylpyridyl)ethylinium directing agent for synthesis of ZSM-35; U.S. Pat. No.4,568,654, teaching use of cobalticinium, dimethylpiperidinium,trimethylene bis trimethylammonium or tetramethylpiperazinium directingagents for synthesis of ZSM-51; U.S. Pat. No. 4,559,213, teaching use ofDABCO-C₄₋₁₀ -diquat directing agent for synthesis of ZSM-12; U.S. Pat.No. 4,482,531, teaching synthesis of ZSM-12 with a DABCO-C_(n) -diquat,n being 4,5,6 or 10, directing agent; and U.S. Pat. No. 4,539,193,teaching use of bis (dimethylpiperidinium) trimethylene directing agentfor synthesis of ZSM-12.

Various diquaternary ammonium compounds have been identified asdirecting agents for a particular assortment of crystalline materials.For instance, U.S. Pat. Nos. 4,490,342 and 4,619,820 show synthesis ofZSM-23 from a reaction mixture containing the organic of U.S. Pat. No.4,531,012, i.e. (CH₃)₃ N⁺ (R)N⁺ (CH₃)₃, where R is a saturated orunsaturated hydrocarbon having 7 carbon atoms. U.S. Pat. No. 4,665,250teaches the use of linear diquaternary ammonium compounds of thestructure (CH₃)₃ N⁺ (Ch₂)_(m) N⁺ (CH₃)₃, m being 5, 6, 8, 9 or 10, forsynthesis of ZSM-48. U.S. Pat. No. 4,623,527 teaches numerousdiquaternary ammonium compounds and shows use of (CH₃)₃ N⁺ (CH₂)₇ N⁺(CH₃)₃ directing agent for synthesis of MCM-10.

U.S. Pat. No. 4,632,815 teaches numerous diquaternary ammonium compoundsand shows use of (CH₃)₃ N⁺ (CH₂)₄ N⁺ (CH₃)₃ to direct synthesis of aSilica-X structure type. U.S. Pat. No. 4,585,639 teaches use of thediquaternary (C₂ H₅)(CH₃)₂ N⁺ (CH₂)_(4or6) N⁺ (CH₃)₂ (C₂ H₅) asdirecting agent for synthesis of ZSM-12. Synthesis of ZSM-5 is directedby the diquaternary (alkyl)₃ N⁺ (CH₂)₆ N⁺ (alkyl)₃, alkyl being propylor butyl, in U.S. Pat. No. 4,585,638.

EPA 42,226 and U.S. Pat. No. 4,537,754 teach existence of numerousdiquaternary ammonium compounds, but show use of (CH₃)₃ N⁺ (CH₂)₆ N⁺(CH₃)₃ as directing agent for synthesis of EU-1. EPA 51,318 teaches useof the same diquaternary for synthesis of TPZ-3. It is noted that EU-1,TPZ-3 and ZSM-50 (synthesized with dibenzyldimethylammonium directingagent) have the same structure.

Applicants know of no prior art method for preparing a highly siliceouscrystalline ferrierite-type structure identified as ZSM-35 utilizing thepresent method.

SUMMARY OF THE INVENTION

An economical and reproducible method for preparing a crystallinematerial identified as ZSM-35 exhibiting high purity, catalytic activityand other valuable properties is provided. The method comprises forminga reaction mixture hydrogel containing sources of alkali or alkalineearth metal (M) cations; an oxide of trivalent element (X), e.g.aluminum, boron, iron, gallium, indium and mixtures thereof; an oxide oftetravalent element (Y), e.g. silicon, germanium, tin and mixturesthereof; a directing agent (R) of 4-aminocyclohexanol; and water, saidreaction mixture having a composition in terms of mole ratios, withinthe following ranges:

    ______________________________________                                        Reactants     Useful    Preferred                                             ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                     1 to 100                                                                              10 to 50                                              H.sub.2 O/YO.sub.2                                                                            10 to 100                                                                             15 to 50                                              OH.sup.- /YO.sub.2                                                                            0 to 0.25                                                                               0 to 0.1                                            M/YO.sub.2      0 to 2.0                                                                              0.10 to 1.0                                           R/YO.sub.2    0.18 to 2.0                                                                             0.18 to 1.0                                           ______________________________________                                    

The method further comprises maintaining the reaction mixture untilcrystals of ZSM-35-type structure are formed. Reaction conditionsrequired consist of heating the foregoing reaction mixture to atemperature of from about 100° C. to about 200° C. for a period of timeof from about 10 hours to about 10 days. A more preferred temperaturerange is from about 130° C. to about 180° C. with the amount of time ata temperature in such range being from about 2 days to about 8 days. Thesolid product comprising ZSM-35 crystals is recovered from the reactionmedium, as by cooling the whole to room temperature, filtering and waterwashing.

EMBODIMENTS

The particular effectiveness of the presently required organic directingagent, i.e. 4-aminocyclohexanol, when compared with other directingagents, such as those identified above, for the present synthesis isbelieved due to its ability to function as a template in the nucleationand growth of ZSM-35 crystals from the above low YO₂, e.g. SiO₂, lowalkalinity, e.g. low OH⁻ /YO₂, reaction mixture. This is true eventhough no predigestion of the gel is required prior to crystallization.This different organic agent functions in this fashion in the reactionmixture having the above described composition and under the abovedescribed conditions of temperature and time. The reaction mixturerequired for this invention is X-rich, e.g. aluminum-rich, with a YO₂/X₂ O₃ molar ratio of from about 1/1 to about 100/1, preferably fromabout 10/1 to about 50/1, most preferably from about 10/1 to about 30/1.

It should be noted that the ratio of components of the reaction mixturerequired herein are critical to achieve maximum effectiveness. Forinstance, if the YO₂ /X₂ O₃ ratio is above about 100, something otherthan ZSM-35-type crystal will form. In general, with higher YO₂ /X₂ O₃ratios in the reaction mixture, crystallization of layered materialincreases and ZSM-35 decreases. Further, at YO₂ /X₂ O₃ molar ratios lessthan about 100/1, the R/YO₂ mole ratio minimum for most successfulZSM-35 synthesis is about 0.18/1. When this ratio drops below about 0.18at the YO₂ /X₂ O₃ ratios of, for example, 21 or less, mixtures oflayered and amorphous materials comprise the product. Still further, formost effective synthesis of ZSM-35 by this method, the OH⁻ /YO₂ ratioshould not be less than 0.

The synthesis of the present invention is facilitated when the reactionmixture comprises seed crystals, such as those having the structure ofZSM-35. The use of at least 0.01%, preferably about 0.10%, and even morepreferably about 1% seed crystals (based on total weight) of crystallinematerial will be useful.

The reaction mixture composition for the synthesis of ZSM-35-typecrystals hereby can be prepared utilizing materials which can supply theappropriate oxide. The useful sources of X₂ O₃, e.g. aluminum oxide,iron oxide and/or boron oxide, include, as non-limiting examples, anyknown form of such oxide, e.g. aluminum oxide or hydroxide, organic orinorganic salt or compound, e.g. alumina, aluminates and borates. Theuseful sources of YO₂, e.g. silicon oxide, include, as non-limitingexamples, known forms of such oxide, e.g. silicic acid or silicondioxide, alkoxy- or other compounds of silicon, including silica gel andsilica hydrosol.

It will be understood that each oxide component utilized in the reactionmixture for this synthesis can be supplied by one or more essentialreactants and they can be mixed together in any order. For example, anyoxide can be supplied by an aqueous solution. The reaction mixture canbe prepared either batchwise or continuously. Crystal size andcrystallization time for the product composition comprising the ZSM-35crystals will vary with the exact nature of the reaction mixtureemployed within the above limitations.

The 4-aminocyclohexanol directing agent for use herein has a formula C₆H₁₃ NO, and may be structurally represented as follows: ##STR1## Thesource of the directing agent may be, for example, the hydrohalide, e.g.chloride or bromide. The cis- or transisomers may be used in combinationor individually.

The ZSM-35 crystal composition prepared hereby has a characteristicX-ray diffraction pattern, including values substantially as set forthin Table 1, hereinafter.

                  TABLE 1                                                         ______________________________________                                        Interplanar d-Spacing (A)                                                                      Relative Intensity (I/I.sub.o)                               ______________________________________                                        11.40 ± 0.1   w                                                            9.55 ± 0.2    m-s                                                          7.07 ± 0.05   m                                                            6.97 ± 0.02   w-m                                                          6.62 ± 0.03   w-m                                                          5.79 ± 0.05   w                                                            5.69 ± 0.03   w                                                            4.00 ± 0.02   s                                                            3.95 ± 0.02   m                                                            3.87 ± 0.03   w                                                            3.78 ± 0.03   m                                                            3.68 ± 0.03   w                                                            3.55 ± 0.03   vs                                                           3.48 ± 0.02   s                                                            3.40 ± 0.05   w                                                            3.31 ± 0.03   w-m                                                          3.15 ± 0.03   w-m                                                          3.07 ± 0.03   w                                                            2.87 ± 0.04   w                                                            ______________________________________                                    

These X-ray diffraction data were collected with a Rigaku diffractionsystem, equipped with a graphite diffracted beam monochromator andscintillation counter, using copper K-alpha radiation. The diffractiondata were recorded by step-scanning at 0.02 degrees of two-theta, wheretheta is the Bragg angle, and a counting time of 1 second for each step.The interplanar spacings, d's, were calculated in Angstrom units (A),and the relative intensities of the lines, I/I_(o), where I_(o) isone-hundredth of the intensity of the strongest line, above background,were derived with the use of a profile fitting routine (or secondderivative algorithm). The intensities are uncorrected for Lorentz andpolarization effects. The relative intensities are given in terms of thesymbols vs=very strong (75-100), s=strong (50-74), m=medium (25-49) andw=weak (0-24). It should be understood that diffraction data listed forthis sample as single lines may consist of multiple overlapping lineswhich under certain conditions, such as differences in crystallite sizesor very high experimental resolution or crystallographic change, mayappear as resolved or partially resolved lines. Typically,crystallographic changes can include minor changes in unit cellparameters and/or a change in crystal symmetry, without a change intopology of the structure. These minor effects, including changes inrelative intensities, can also occur as a result of differences incation content, framework composition, nature and degree of porefilling, and thermal and/or hydrothermal history.

The crystalline ZSM-35 prepared hereby has a composition involving themolar relationship:

    X.sub.2 O.sub.3 :(y)YO.sub.2

wherein X is a trivalent element, such as aluminum, boron, iron, indiumand/or gallium, preferably aluminum; Y is a tetravalent element, such assilicon, tin and/or germanium, preferably silicon; and y is from about 1to about 100, usually from about 10 to about 50, more usually from about10 to about 30. In the as-synthesized form, the crystalline material hasa formula, on an anhydrous basis and in terms of moles of oxides per ymoles of YO₂, as follows:

    (0.4 to 0.6)M.sub.2 O:(0.4 to 0.6)R:X.sub.2 O.sub.3 :(y)YO.sub.2

wherein M and R are as defined above. The M and R components areassociated with the material as a result of their presence duringcrystallization, and are easily removed by post-crystallization methodshereinafter more particularly described.

Synthetic ZSM-35-type crystals prepared in accordance herewith can beused either in the as-synthesized form, the hydrogen form or anotherunivalent or multivalent cationic form. It can also be used in intimatecombination with a hydrogenating component such as tungsten, vanadium,molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noblemetal such as platinum or palladium where ahydrogenation-dehydrogenation function is to be performed. Suchcomponents can be exchanged into the composition, impregnated therein orphysically intimately admixed therewith. Such components can beimpregnated in or on to the ZSM-35 such as, for example, by, in the caseof platinum, treating the material with a platinum metal-containing ion.Suitable platinum compounds for this purpose include chloroplatinicacid, platinous chloride and various compounds containing the platinumamine complex. Combinations of metals and methods for their introductioncan also be used.

Synthetic ZSM-35 crystals, when employed either as an adsorbent or as acatalyst in a hydrocarbon conversion process, should be dehydrated atleast partially. This can be done by heating to a temperature in therange of from about 65° C. to about 315° C. in an inert atmosphere, suchas air, nitrogen, etc. and at atmospheric or subatmospheric pressuresfor between 1 and 48 hours. Dehydration can be performed at lowertemperature merely by placing the zeolite in a vacuum, but a longer timeis required to obtain a particular degree of dehydration. The thermaldecomposition product of the newly synthesized ZSM-35 can be prepared byheating same at a temperature of from about 20° C. to about 550° C. forfrom 1 hour to about 48 hours.

The original cations, e.g. alkali or alkaline earth metal, of theas-synthesized material can be replaced in accordance with techniqueswell known in the art, at least in part, by ion exchange with othercations. Preferred replacing cations include metal ions, hydrogen ions,hydrogen precursor, e.g. ammonium, ions and mixtures thereof.Particularly preferred cations are those which render the materialcatalytically active, especially for certain hydrocarbon conversionreactions. These include hydrogen, rare earth metals and metals ofGroups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of the Periodic Tableof the Elements, especially gallium, indium and tin.

Typical ion exchange technique would be to contact the synthetic ZSM-35material with a salt of the desired replacing cation or cations.Examples of such salts include the halides, e.g. chlorides, nitrates andsulfates.

Representative ion exchange techniques are disclosed in a wide varietyof patents including U.S. Pat. Nos. 3,140,249; 3,140,251; and 3,140,253.

Following contact with the salt solution of the desired replacingcation, the ZSM-35 is then preferably washed with water and dried at atemperature ranging from 65° C. to about 315° C. and thereafter may becalcined in air or other inert gas at temperatures ranging from about200° C. to about 550° C. for periods of time ranging from 1 to 48 hoursor more to produce a catalytically-active thermal decomposition productthereof.

The crystalline ZSM-35 prepared by the instant invention is formed in awide variety of particle sizes. Generally speaking, the particles can bein the form of a powder, a granule, or a molded product, such asextrudate having particle size sufficient to pass through a 2 mesh(Tyler) screen and be retained on a 400 mesh (Tyler) screen. In caseswhere the catalyst is molded, such as by extrusion, the crystallinematerial can be extruded before drying or dried or partially dried andthen extruded.

In the case of many catalysts, it is desired to incorporate the crystalshereby prepared with another material resistant to the temperatures andother conditions employed in certain organic conversion processes. Suchmatrix materials include active and inactive materials and synthetic ornaturally occurring zeolites as well as inorganic materials such asclays, silica and/or metal oxides, e.g. alumina, titania and/orzirconia. The latter may be either naturally occurring or in the form ofgelatinous precipitates, sols or gels including mixtures of silica andmetal oxides. Use of a material in conjuction with the ZSM-35, i.e.combined therewith, which is active, may enhance the conversion and/orselectivity of the catalyst in certain organic conversion processes.Inactive materials suitably serve as diluents to control the amount ofconversion in a given process so that products can be obtainedeconomically and orderly without employing other means for controllingthe rate or reaction. Frequently, crystalline catalytic materials havebeen incorporated into naturally occurring clays, e.g. bentonite andkaolin. These materials, i.e. clays, oxides, etc., function, in part, asbinders for the catalyst. It is desirable to provide a catalyst havinggood crush strength because in a petroleum refinery the catalyst isoften subjected to rough handling, which tends to break the catalystdown into powder-like materials which cause problems in processing.

Naturally occurring clays which can be composited with the herebysynthesized crystalline material include the montmorillonite and kaolinfamilies which include the subbentonites, and the kaolins commonly knownas Dixie, McNamee, Georgia and Florida clays, or others in which themain mineral constituent is halloysite, kaolinite, dickite, nacrite oranauxite. Such clays can be used in the raw state as originally mined orinitially subjected to calcination, acid treatment or chemicalmodification.

In addition to the foregoing materials, the present crystals can becomposited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania, as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesiaand silica-magnesia-zirconia. The matrix can be in the form of a cogel.A mixture of these components could also be used.

The relative proportions of finely divided crystalline material andmatrix vary widely with the crystalline material content ranging fromabout 1 to about 90 percent by weight, and more usually in the range ofabout 2 to about 50 percent by weight of the composite.

Employing a catalytically active form of the catalyst of this inventionwhich may contain additional hydrogenation components, reforming stockscan be reformed employing a temperature between about 370° C. and about540° C. The pressure can be between about 100 psig and about 1000 psig,but it is preferably between about 200 psig and about 700 psig. Theliquid hourly space velocity is generally between about 0.1 and about 10hr⁻¹ preferably between about 0.5 and about 4 hr⁻¹, and the hydrogen tohydrocarbon mole ratio is generally between about 1 and about 20,preferably between about 4 and about 12.

The catalyst can also be used for hydroisomerization of normalparaffins, when provided with a hydrogenation component, e.g. platinum.Hydroisomerization is carried out at a temperature between about 90° C.and 375° C., preferably about 145° C. to about 290° C., with a liquidhourly space velocity between about 0.01 and about 2 hr⁻¹, preferablybetween about 0.25 and about 0.50 hr⁻¹, employing hydrogen such that thehydrogen to hydrocarbon mole ratio is between about 1:1 and about 5:1.

The catalyst can also be used for reducing the pour point of gas oils.This reaction may be conducted at a liquid hourly space velocity betweenabout 10 and about 30 hr⁻¹ and at a temperature between about 400° C.and about 540° C.

Other reactions which can be accomplished employing the catalyst of thisinvention containing a metal, e.g. platinum, includehydrogenation-dehydrogenation reactions and desulfurization reactions.

In order to more fully illustrate the nature of the invention and themanner of practicing same, the following examples are presented. In theexamples, whenever adsorption data are set forth for comparison ofsorptive capacities for water, cyclohexane and n-hexane, they aredetermined as follows:

A weighed sample of the calcined adsorbant is contacted with the desiredpure adsorbate vapor in an adsorption chamber, evacuated to 1 mm andcontacted with 12 mm Hg of water vapor or 20 mm Hg of n-hexane, orcyclohexane vapor, pressures less than the vapor-liquid equilibriumpressure of the respective adsorbate at room temperature. The pressureis kept constant (within about ±0.5 mm) by addition of absorbate vaporcontrolled by a manostat during the adsorption period, which does notexceed about 8 hours. As adsorbate is adsorbed by the sorbant material,the decrease in pressure causes the manostat to open a valve whichadmits more adsorbate vapor to the chamber to restore the above controlpressures. Sorption is complete when the pressure change is notsufficient to activate the manostat. The increase in weight iscalculated as the adsorption capacity of the sample in g/100 g ofcalcined adsorbant.

When Alpha Value is examined, it is noted that the Alpha Value is anapproximate indication of the catalytic cracking activity of thecatalyst compared to a standard catalyst and it gives the relative rateconstant (rate of normal hexane conversion per volume of catalyst perunit time). It is based on the activity of silica-alumina crackingcatalyst taken as an Alpha of 1 (Rate Constant=0.016 sec⁻¹). The AlphaTest is described in U.S. Pat. No. 3,354,078; in the Journal ofCatalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p.395 (1980), each incorporated herein by reference as to thatdescription. The experimental conditions of the test used herein includea constant temperature of 538° C. and a variable flow rate as describedin detail in the Journal of Catalysis, Vol. 61, p. 395.

EXAMPLE 1

To water (47.248 g) was added sodium aluminate (1.444 g, technicalgrade, 74% solids), and sodium hydroxide (2.465 g). This mixture wasstirred briefly to complete dissolution, then trans-4-aminocyclohexanolhydrochloride (7.320 g) was added. To this solution was added silica(Ultrasil, 9.149 g), and the resulting gel was transferred to a teflonliner, placed in an autoclave, pressurized (100 psig), sealed, thenheated (145° C.) with stirring (.sup.˜ 335 rpm) for 1 week. The finalhydrogel is described by the mole ratios as follows:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3 =                                                           21.36                                                               OH.sup.- /SiO.sub.2 =                                                                   0                                                                   R/SiO.sub.2 =                                                                           0.34                                                                H.sub.2 O/SiO.sub.2 =                                                                   19.02                                                               Na.sup.+ /SiO.sub.2 =                                                                   0.54                                                         ______________________________________                                    

After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (9.066 g). The X-raydiffraction pattern (λ=1.5418) of the product proved it to becrystalline ZSM-35, and is shown in Table 2.

A portion of the as-synthesized product of this example was calcined at538° C. for 10 hours. Table 3 shows the X-ray diffraction pattern ofthis calcined ZSM-35 material.

                  TABLE 2                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        19.99            4.42    9.96                                                 11.42            7.74    8.87                                                 9.51             9.30    43.80                                                7.09            12.48    34.97                                                6.96            12.72    14.15                                                6.83            12.96    4.23                                                 6.63            13.36    19.03                                                5.78            15.32    12.04                                                5.70            15.54    11.87                                                4.99            17.76    6.34                                                 4.96            17.88    5.98                                                 4.83            18.36    5.61                                                 4.00            22.24    56.81                                                3.95            22.50    25.70                                                3.86            23.04    21.51                                                3.79            23.46    47.21                                                3.67            24.24    18.38                                                3.55            25.08    100.00                                               3.48            25.58    71.41                                                3.39            26.32    11.83                                                3.32            26.82    26.23                                                3.20            27.86    4.84                                                 3.14            28.42    21.47                                                3.06            29.18    15.29                                                2.96            30.18    7.40                                                 2.94            30.38    5.41                                                 2.90            30.82    10.57                                                2.86            31.30    4.11                                                 2.82            31.70    10.37                                                2.72            32.98    7.32                                                 2.65            33.80    8.95                                                 2.59            34.66    5.90                                                 ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        9.51             9.30    61.03                                                7.08            12.50    50.89                                                6.96            12.72    34.11                                                6.61            13.40    35.47                                                5.76            15.38    10.10                                                5.67            15.62    15.60                                                3.99            22.30    55.25                                                3.94            22.58    26.69                                                3.85            23.08    17.64                                                3.78            23.54    45.11                                                3.72            23.86    14.51                                                3.66            24.34    16.46                                                3.54            25.18    100.00                                               3.47            25.66    64.48                                                3.42            26.08    7.19                                                 3.38            26.40    12.19                                                3.31            26.90    22.37                                                3.13            28.48    25.42                                                3.05            29.30    15.19                                                2.95            30.28    9.28                                                 2.89            30.92    11.32                                                2.83            31.64    8.82                                                 2.71            33.10    8.28                                                 2.64            33.92    9.37                                                 2.58            34.78    5.32                                                 2.57            34.92    5.09                                                 ______________________________________                                    

The calcined product of this example has an Alpha Value of 420, and thefollowing equilibrium adsorption capacities in grams/100 grams:

    ______________________________________                                               H.sub.2 O                                                                              9.0                                                                  Cyclohexane                                                                            1.0                                                                  n-Hexane 5.4                                                           ______________________________________                                    

EXAMPLE 2

To water (47.248 g) was added sodium aluminate (0.289 g, technicalgrade, 74% solids) and sodium hydroxide (2.443 g). This mixture wasstirred briefly to complete dissolution, then trans-4-aminocyclohexanolhydrochloride (7.316 g) was added. To this solution was added silica(Ultrasil, 9.154 g), and the resulting gel was transferred to a teflonliner, placed in an autoclave, pressurized (100 psig), sealed, thenheated (145° C.) with stirring (.sup.˜ 340 rpm) for 1 week. The finalhydrogel had the following composition in terms of mole ratios:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3 =                                                           101.79                                                              OH.sup.- /SiO.sub.2 =                                                                   0.07                                                                R/SiO.sub.2 =                                                                           0.34                                                                H.sub.2 O/SiO.sub.2 =                                                                   18.89                                                               Na.sup.+ /SiO.sub.2 =                                                                   0.46                                                         ______________________________________                                    

After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (8.916 g). The X-raydiffraction pattern (λ=1.5418) of the product proved it to be a layeredmaterial devoid of any ZSM-35 as shown in Table 4.

A portion of the as-synthesized product of this example was calcined at538° C. for 10 hours. Table 5 shows the X-ray diffraction pattern ofthis calcined material.

                  TABLE 4                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        19.99            4.42    100.00                                               15.67            5.64    11.05                                                9.98             8.86    29.60                                                9.53             9.28    26.97                                                7.29            12.14    6.27                                                 7.09            12.48    11.17                                                6.95            12.74    7.29                                                 6.62            13.38    8.49                                                 5.76            15.38    6.86                                                 5.68            15.60    7.54                                                 4.97            17.84    21.13                                                4.84            18.34    7.53                                                 4.72            18.80    9.21                                                 4.53            19.58    5.76                                                 4.27            20.80    8.44                                                 4.21            21.10    6.59                                                 4.12            21.58    7.57                                                 3.99            22.26    27.84                                                3.85            23.10    12.79                                                3.79            23.50    19.49                                                3.66            24.32    17.74                                                3.55            25.10    41.16                                                3.44            25.90    63.37                                                3.33            26.80    38.31                                                3.21            27.82    40.31                                                3.14            28.42    13.60                                                3.05            29.26    9.65                                                 2.95            30.30    11.37                                                2.91            30.70    7.34                                                 2.90            30.88    7.75                                                 2.83            31.66    12.85                                                2.65            33.80    5.62                                                 ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        18.18            4.86    47.66                                                9.37             9.44    86.34                                                7.02            12.60    40.21                                                6.91            12.82    35.98                                                6.60            13.50    31.89                                                5.62            15.76    19.33                                                5.38            16.46    14.89                                                5.01            17.70    21.79                                                4.71            18.84    18.56                                                3.96            22.44    57.36                                                3.91            22.76    39.47                                                3.82            23.28    33.54                                                3.75            23.70    47.44                                                3.64            24.46    36.47                                                3.52            25.30    88.35                                                3.45            25.82    100.00                                               3.39            26.26    85.50                                                3.30            27.04    51.79                                                3.21            27.78    26.71                                                3.12            28.66    33.37                                                3.03            29.48    24.43                                                2.96            30.14    15.38                                                2.94            30.44    17.51                                                2.88            31.08    17.93                                                2.82            31.72    20.55                                                2.63            34.06    13.49                                                ______________________________________                                    

EXAMPLE 3

To water (25.435 g) was added sodium aluminate (0.776 g, technicalgrade, 74% solids) and sodium hydroxide (0.669 g). This mixture wasstirred briefly to complete dissolution, then 1.976 g oftrans-4-aminocyclohexanol hydrochloride was added. To this solution wasadded silica (Ultrasil, 4.918 g), and the resulting gel was transferredto a teflon liner, placed in an autoclave, pressurized (100 psig),sealed, then heated (145° C.) without stirring for 1 week. The finalhydrogel had the following composition in terms of mole ratios:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3 =                                                           21.36                                                               OH.sup.- /SiO.sub.2 =                                                                   -0.04                                                               R/SiO.sub.2 =                                                                           0.17                                                                H.sub.2 O/SiO.sub.2 =                                                                   19.05                                                               Na.sup.+ /SiO.sub.2 =                                                                   0.32                                                         ______________________________________                                    

After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (5.09 g). The X-raydiffraction pattern (λ=1.5418) of the product proved it to be a mixedlayered and amorphous material, instead of ZSM-35, as shown in Table 6.

                  TABLE 6                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        9.39             9.42    48.55                                                7.04            12.58    32.31                                                6.56            13.50    27.72                                                5.70            15.54    31.16                                                3.98            22.36    98.69                                                3.85            23.08    86.55                                                3.77            23.58    96.23                                                3.65            24.36    79.61                                                3.53            25.22    100.00                                               3.46            25.74    85.46                                                3.31            26.92    62.49                                                3.25            27.46    55.93                                                3.14            28.44    54.62                                                3.05            29.32    46.80                                                2.81            31.80    50.96                                                ______________________________________                                    

EXAMPLE 4

To water (25.429 g) was added sodium hydroxide (1.293 g). This mixturewas stirred briefly to complete dissolution, thentrans-4-aminocyclohexanol hydrochloride (3.921 g) was added. To thissolution was added silica (Ultrasil, 4.918 g), and the resulting gel wastransferred to a teflon liner, placed in an autoclave, pressurized (100psig), sealed, then heated (145° C.) without stirring for 1 week. Thefinal hydrogel is described by the moles ratios as follows:

    ______________________________________                                        SiO.sub.2 /Al.sub.2 O.sub.3 =                                                                 1745.14                                                       OH.sup.- /SiO.sub.2 =                                                                         0.08                                                          R/SiO.sub.2 =   0.34                                                          H.sub.2 O/SiO.sub.2 =                                                                         18.90                                                         Na.sup.+ /SiO.sub.2 =                                                                         0.44                                                          ______________________________________                                    

After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (4.771 g). The X-raydiffraction pattern (λ=1.5418) of the product proved it to be a layeredmaterial, instead of ZSM-35, as shown in Table 7.

                  TABLE 7                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        19.54            4.52    20.21                                                15.18            5.82    84.55                                                7.68            11.52    14.03                                                7.19            12.30    9.51                                                 6.81            13.00    8.40                                                 6.30            14.04    8.16                                                 5.13            17.26    23.85                                                4.94            17.94    18.07                                                4.43            20.02    24.01                                                3.99            22.25    24.41                                                3.61            24.64    30.11                                                3.54            25.10    32.96                                                3.42            26.00    100.00                                               3.29            27.10    53.17                                                3.13            28.44    66.56                                                2.97            30.00    13.95                                                2.81            31.82    14.26                                                2.71            33.06    9.67                                                 2.62            34.11    11.09                                                2.58            34.76    12.76                                                ______________________________________                                    

EXAMPLE 5

To water (47.208 g) was added sodium aluminate (1.443 g, technicalgrade, 74% solids) and sodium hydroxide (2.493 g). This mixture wasstirred briefly to complete dissolution, then trans-4-aminocyclohexanolhydrochloride (7.392 g) was added. To this solution was added silica(Ultrasil, 9.179 g), and the resulting gel was transferred to a teflonliner, placed in an autoclave, pressurized (100 psig), sealed, thenheated (175° C.) with stirring (.sup.˜ 340 rpm) for 3 days. The finalhydrogel is described by the moles ratios as follows:

    ______________________________________                                               SiO.sub.2 /Al.sub.2 O.sub.3 =                                                           21.44                                                               OH.sup.- /SiO.sub.2 =                                                                   0                                                                   R/SiO.sub.2 =                                                                           0.34                                                                H.sub.2 O/SiO.sub.2 =                                                                   18.94                                                               Na.sup.+ /SiO.sub.2 =                                                                   0.54                                                         ______________________________________                                    

After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (8.223 g). The X-raydiffraction pattern (λ=1.5418) of the product proved it to becrystalline ZSM-35, as shown in Table 8.

A portion of the as-synthesized product of this example was calcined at538° C. for 10 hours. Table 9 shows the X-ray diffraction pattern ofthis calcined ZSM-35 material.

                  TABLE 8                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        11.36            7.78    7.99                                                 9.51             9.30    48.76                                                9.08             9.74    5.57                                                 7.09            12.48    37.32                                                6.97            12.70    12.78                                                6.62            13.38    17.53                                                5.79            15.30    12.22                                                5.68            15.60    12.97                                                4.97            17.84    5.13                                                 4.84            18.34    5.27                                                 4.52            19.64    3.04                                                 4.26            20.84    5.48                                                 4.00            22.24    58.61                                                3.95            22.52    25.28                                                3.86            23.04    21.35                                                3.79            23.48    50.19                                                3.74            23.76    8.34                                                 3.67            24.26    19.19                                                3.55            25.10    100.00                                               3.48            25.58    65.35                                                3.39            26.30    13.59                                                3.35            26.60    22.17                                                3.32            26.84    26.69                                                3.21            27.74    1.06                                                 3.14            28.42    19.67                                                3.06            29.22    17.98                                                2.96            30.20    7.34                                                 2.94            30.38    4.63                                                 2.90            30.82    10.67                                                2.85            31.38    3.82                                                 2.82            31.70    3.91                                                 2.82            31.72    3.91                                                 2.71            33.02    6.14                                                 2.65            33.80    9.13                                                 2.62            34.22    2.91                                                 2.59            34.66    5.55                                                 ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        9.51             9.30    83.69                                                9.08             9.74    9.34                                                 7.08            12.50    55.21                                                6.96            12.72    37.95                                                6.61            13.40    38.84                                                5.77            15.36    11.26                                                5.67            15.64    17.12                                                4.76            18.66    4.74                                                 4.27            20.80    6.90                                                 3.99            22.30    61.59                                                3.94            22.58    31.95                                                3.85            23.10    20.55                                                3.78            23.56    50.29                                                3.73            23.84    11.96                                                3.66            24.32    19.23                                                3.54            25.18    100.00                                               3.47            25.66    66.30                                                3.35            26.58    24.53                                                3.31            26.92    25.39                                                3.22            27.66    5.07                                                 3.13            28.50    25.34                                                3.05            29.28    17.65                                                2.95            30.28    9.24                                                 2.89            30.94    12.26                                                2.71            33.10    7.39                                                 2.64            33.92    8.75                                                 2.58            34.82    5.36                                                 ______________________________________                                    

The calcined product of this example proves to have an Alpha Value of420, the following equilibrium adsorption capacities in grams/100 grams:

    ______________________________________                                               H.sub.2 O                                                                              9.0                                                                  Cyclohexane                                                                            1.0                                                                  n-Hexane 5.4                                                           ______________________________________                                    

These examples demonstrate the present invention of synthesizing ZSM-35from the required reaction mixture having a low alkalinity, low YO₂ /X₂O₃ molar ratio and directing agent of 4-aminocyclohexanol. When the YO₂/X₂ O₃ ratio in the reaction mixture is greater than about 100,something other than ZSM-35 forms. Synthesis conditions using a YO₂ /X₂O₃, e.g. SiO₂ /Al₂ O₃, ratio at about 101 produced a layered material.Synthesis conditions using YO₂ /X₂ O₃, e.g. SiO₂ /Al₂ O₃, ratio near 21with an R/YO₂ ratio less than 0.18 produced a mixture of layered andamorphous material instead of crystalline ZSM-35.

Changes and modifications in the specifically described embodiments canbe carried out without departing from the scope of the invention whichis intended to be limited only by the scope of the appended claims.

What is claimed is:
 1. A method for synthesizing crystalline materialexhibiting a characteristic X-ray diffraction pattern includingd-spacing maxima values as follows:

    ______________________________________                                        Interplanar d-spacing, (A)                                                                     Relative Intensity (I/I.sub.o)                               ______________________________________                                        11.40 ± 0.1   w                                                            9.55 ± 0.2    m-s                                                          7.07 ± 0.05   m                                                            6.97 ± 0.02   w-m                                                          6.62 ± 0.03   w-m                                                          5.79 ± 0.05   w                                                            5.69 ± 0.03   w                                                            4.00 ± 0.02   s                                                            3.95 ± 0.02   m                                                            3.87 ± 0.03   w                                                            3.78 ± 0.03   m                                                            3.68 ± 0.03   w                                                            3.55 ± 0.03   vs                                                           3.48 ± 0.02   s                                                            3.40 ± 0.05   w                                                            3.31 ± 0.03   w-m                                                          3.15 ± 0.03   w-m                                                          3.07 ± 0.03   w                                                            2.87 ± 0.04   w                                                            ______________________________________                                    

where vs=very strong (75-100), s=strong (50-74), m=medium (25-49) andw=weak (0-24), which comprises (i) preparing a mixture capable offorming said material, said mixture comprising sources of alkali oralkaline earth metal (M), an oxide of trivalent element (X), an oxide oftetravalent element (Y), water and directing agent (R) of4-aminocyclohexanol, and having a composition, in terms of mole ratios,within the following ranges:

    ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                    1 to 100                                                       H.sub.2 O/YO.sub.2                                                                          10 to 100                                                       OH.sup.- /YO.sub.2                                                                            0 to 0.25                                                     M/YO.sub.2     0 to 2.0                                                       R/YO.sub.2    0.18 to 2.0                                                     ______________________________________                                    

(ii) maintaining said mixture under sufficient conditions including atemperature of from about 100° C. to about 200° C. until crystals ofsaid material are formed; and (iii) recovering said crystalline materialfrom step (ii), said recovered crystalline material containing said R.2. The method of claim 1 wherein said mixture has the followingcomposition ranges:

    ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                            10 to 50                                               H.sub.2 O/YO.sub.2     15 to 50                                               OH.sup.- /YO.sub.2     0 to 0.1                                               M/YO.sub.2           0.10 to 1.0                                              R/YO.sub.2           0.18 to 1.0.                                             ______________________________________                                    


3. The method of claim 1 wherein said mixture further comprises seedcrystals in sufficient amount to enhance synthesis of said crystallinematerial.
 4. The method of claim 3 wherein said seed crystals have thestructure of ZSM-
 35. 5. The method of claim 1 wherein said X isaluminum, boron, iron, gallium, indium or a mixture thereof, and said Yis silicon, germanium, tin or a mixture thereof.
 6. The method of claim1 wherein X comprises aluminum and Y comprises silicon.
 7. A mixturecapable of forming crystals of ZSM-35 structure upon crystallization,said mixture comprising sources of alkali or alkaline earth metal (M),trivalent element (X) oxide selected from the group consisting of oxideof aluminum, boron, iron, gallium, indium and mixtures thereof;tetravalent element (Y) oxide selected from the group consisting ofoxide of silicon, germanium, tin and mixtures thereof; water anddirecting agent (R) of 4-aminocyclohexanol, and having a composition, interms of mole ratios, within the following ranges:

    ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                            1 to 100                                               H.sub.2 O/YO.sub.2     10 to 100                                              OH.sup.- /YO.sub.2     0 to 0.25                                              M/YO.sub.2             0 to 2.0                                               R/YO.sub.2           0.18 to 2.0.                                             ______________________________________                                    


8. The method of claim 1 comprising replacing ions of the crystallinematerial recovered in step (iii), at least in part, by ion exchange withan ion or a mixture of ions selected from the group consisting ofhydrogen and hydrogen precursors, rare earth metals and metals fromGroups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB and VIII of the PeriodicTable of Elements.
 9. The method of claim 2 comprising replacing ions ofthe crystalline material recovered in step (iii), at least in part, byion exchange with an ion or a mixture of ions selected from the groupconsisting of hydrogen and hydrogen precursors, rare earth metals andmetals from Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB and VIII ofthe Periodic Table of Elements.
 10. The method of claim 8 wherein saidreplacing ion is hydrogen or a hydrogen precursor.
 11. The method ofclaim 9 wherein said replacing ion is hydrogen or a hydrogen precursor.12. The recovered crystalline material of claim
 1. 13. The recoveredcrystalline material of claim
 2. 14. The R-containing productcrystalline material of claim
 8. 15. The R-containing productcrystalline material of claim
 9. 16. The R-containing productcrystalline material of claim
 10. 17. The R-containing productcrystalline material of claim 11.